Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references (leaves 225-235). Available also in a digital version from Dissertation Abstracts.

Morphology is the origin of life and function. Defining and designing morphology, understanding the relationship between morphology and function, is an essential theme in a number of research areas. In conjugated polymer research, the major obstacles to achieving these goals are the heterogeneity and complexity of conjugated polymer films. In the study presented in this dissertation, various single molecule spectroscopy techniques were used as an approach to minimize the complexity of these problems. By using excitation polarization spectroscopy, it was discovered that single chains of poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) assume a highly ordered rod conformation despite the fact that the morphology of bulk films is known to be amorphous. The comparison of results from experiments and a coarse grained bead-on-a-chain simulation suggested that single chains have the ability to use a thermally induced defect to maximize [pi]-[pi] stacking and adopt a rod conformation as a stable conformation. Bias-induced centroid spectroscopy (BIC) on highly ordered single chains demonstrated that the energy transfer scale could be an order of magnitude larger than the value typically measured for bulk films. It was further demonstrated that such an extraordinary long energy transfer was not a unique property of single chains but was also observed in aggregates as long as the morphology was ordered. These studies were extended to another model compound poly(3-hexylthiophene) (P3HT) to generalize the mechanism of morphology formation and the structure-property relationship. For P3HT, it was shown that side-chains were a very important factor in determining single chain conformation, while the conformation of MEH-PPV was not affected by side-chains. By controlling the side-chains, both ordered and disordered P3HT chains were obtained. The comparison of results from experiments and an energy transfer model simulation quantified that energy transfer was at least twice as efficient in ordered chains as in disordered chains. In aggregates, the difference between the energy transfer efficiency of ordered and disordered morphology was even larger than that in the case of single chains. These results could suggest that there is a very fast energy transfer mechanism that occurs through interchain interactions when chains are packed in ordered fashion. / text

Nanosecond time-resolved resonance Raman (ns-TR3) spectroscopy was used in this thesis to study the photoreduction reactions and the photochemistry of chloro-substituted benzophenone (ClBP) triplets. The 3-chlorobenzophenone (3-ClBP), 4-chlorobenzophenone (4-ClBP) and 4,4′-dichlorobenzophenone (4,4′-diClBP) triplets exhibit similar properties to the parent BP triplet. In isopropyl alcohol (IPA), the hydrogen abstraction reactions were observed for the 3-ClBP, 4-ClBP and 4,4′-diDlBP triplets. The diphenylketyl (DPK) radicals produced from the hydrogen abstraction reactions were observed and the recombination of the DPK and dimethylketyl radicals at the para-position was observed to form a light absorption transient (LAT) species. In MeCN:H2O/1:1 aqueous solutions, these DPK radicals were also observed but with a slower formation rate and the LAT species was produced by reaction with OH radicals. Density functional theory (DFT) calculations were employed to help identify the intermediates seen in the TR3 spectra and to help provide information about the vibrational motions of the molecules examined. The 2-Cl-DPK radical was also observed in the TR3 spectra obtained in an IPA solvent. However, the yield of the 2-Cl-DPK radical and the hydrogen abstraction rate was observed to be significantly lower than that of the other ClBP examined here under the same experimental conditions. The results DFT calculations show that the 2-chloro substituent changes the geometry and the electron density of the molecular orbitals of the BP triplet so that the 2-chloro substituent reduces the hydrogen abstraction ability the triplet state, which is different the hypothesis put forward by some previous studies that an electron-withdrawing group should increase the photoreduction ability of BP derivatives. Norfloxacin (NF) and Enoxacin (EN) are representative derivatives of Fluoroquinolones (FQ). There are four forms of NF and EN and these different forms can coexist in aqueous solutions. The UV-vis absorption and resonance Raman (RR) spectra of NF and EN have been obtained in neat acetonitrile (MeCN), MeCN:HClO4-H2O/1:1 (pH?1), MeCN:H2O/1:1 (pH?7.5) and MeCN:NaOH-H2O/1:1 (pH?13) solutions. The species observed in the spectra are assigned by comparison of the experimental spectra to the DFT calculated spectra and the vibrational modes are also described from the results of the DFT calculations. The absorption spectra of NF and EN obtained in MeCN:H2O/1:1 solutions show that some other species coexist with the tautomeric forms in the neutral aqueous solution. The RR spectra of the tautomeric forms of NF and EN were obtained by subtraction of the RR spectra of the neutral and anionic forms from the RR spectra of NF and EN in neutral aqueous solutions. The results suggest that NF and EN exists in neutral, anionic and tautomeric forms in neutral aqueous solutions. The time dependant DFT calculation results suggest that the fluorine atom has little contribution to the lowest unoccupied molecular orbitals of the different forms of NF and EN. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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Thesis (MTech. degree in Chemistry)--Tshwane University of Technology, 2010. / Discusses an accurate and sensitive method for the determination of trace levels of mercury in environmental air samples may be established using cost effective technologies.

No description available.

We present the observations, reduction and preliminary analysis of a sample of 45 mid-to-high redshift galaxy clusters imaged with the Spitzer Space Telescope's MIPS camera at 24 ~m and selected from the Red Sequence Cluster Survey. The purpose of the data set is motivated by a broad review of studies into the evolutionary trends of galaxy clusters and their constituent galaxy populations, focusing specifically on recent results that indicate clusters are environmental drivers of dusty starburst and active galactic nuclei activity. To accommodate the large amount of data in hand, we have constructed an extensive data reduction pipeline for the MIPS data and describe its development and output in detail. Using the resulting catalogues for introductory analysis, we find strong evidence for an excess luminous infrared galaxy population in galaxy clusters at high redshift and discuss the implications of this discovery in terms of cluster evolution and motivate future work.

The prospect of finding life outside Earth has fascinated mankind for ages, and new technology continuously pushes the boundary of how remote and how obscure evidence we can find. Employing smaller, or completely new, types of landers and robots, and equipping them with miniature instruments would indeed revolutionize exploration of other planets and moons. In this thesis, microsystems technology is used to create a miniature high-precision isotope-resolving molecular spectrometer utilizing the optogalvanic effect. The heart of the instrument, as well as this thesis, is a microplasma source. The plasma source is a split-ring resonator, chosen for its simplicity, pressure range and easily accessible plasma, and modified to fit the challenging application, e.g., by the adding of an additional ground plane for improved electromagnetic shielding, and the integration of microscopic plasma probes to extract the pristine optogalvanic signal. Plasma sources of this kind have been manufactured in both printed circuit board and alumina, the latter for its chemical inertness and for compatibility with other devices in a total analysis system. From previous studies, classical optogalvanic spectroscopy (OGS), although being very sensitive, is known to suffer from stability and reproducibility issues. In this thesis several studies were conducted to investigate and improve these shortcomings, and to improve the signal-to-noise ratio. Moreover, extensive work was put into understanding the underlying physics of the technique. The plasma sources developed here, are the first ever miniature devices to be used in OGS, and exhibits several benefits compared to traditional solutions. Furthermore, it has been confirmed that OGS scales well with miniaturization. For example, the signal strength does not decrease as the volume is reduced like in regular absorption spectroscopy. Moreover, the stability and reproducibility are greatly increased, in some cases as much as by two orders of magnitude, compared with recent studies made on a classical OGS setup. The signal-to-noise ratio has also been greatly improved, e.g., by enclosing the sample cell and by biasing the plasma. Another benefit of a miniature sample cell is the miniscule amount of sample it requires, which can be important in many applications where only small amounts of sample are available. To conclude: With this work, an important step toward a miniature, yet highly performing, instrument for detection of extraterrestrial life, has been taken.

Some physicochemical properties of several series of transition metal chalcocarbonyls such as ((eta)('6)-C(,6)H(,6))Cr(CO)(,2)(CX) and Cr(CO)(,5)(CX) (X = O, S, Se) have been investigated. In particular, the infrared, ('13)C and ('17)O nuclear magnetic resonance and ultraviolet spectra have been examined. The results show that the order of (sigma)-donor and (pi)-acceptor capabilities of the ligands is CO CS. The M((pi)) (--->) CX((pi)*) ultraviolet charge-transfer bands are shown to correlate with the respective (mu)'(,MCX) and ('13)C NMR data. Also, the ('13)C NMR chemical shifts and GQVFF force constants are found to be highly correlated. The ('17)O NMR spectra of the metal chalcocarbonyl complexes display chemical shifts in the opposite direction to the corresponding ('13)C ones. No correlation is found between the ('17)O shieldings and the other spectroscopic data. Reaction of Cr(CO)(,5)(CX) (X = S, Se) with halide ions (Y('-)) afforded mixtures of {Cr(CO)(,5)Y}('-) and trans-{Cr(CO)(,4)(CX)Y}('-) while Cr(CO)(,5)(CS) reacted with cyclohexylamine to give Cr(CO)(,5)(CNC(,6)H(,11)). The similarities and differences in the physicochemical behaviour of the metal chalcocarbonyls compared to related systems are discussed in the light of the different bonding patterns.

Thin coatings of photoresponsive, pyrimidine-terminated molecules, attached to gold or quartz substrates in contact with water, undego photodimerisation and wettability changes when irradiated with UV light at 280 and 240mm. Spin-casting and chemisorption techniques were used to prepare the thin films. / Thesis (PhDApSc)--University of South Australia, 2000.